CN102509633B - High-entropy mixed oxide electrode material and preparing method thereof - Google Patents
High-entropy mixed oxide electrode material and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a high-entropy mixed oxide electrode material and a preparing method thereof, which relate to oxide materials and a process for material preparation. The high-entropy mixed oxide electrode material is composed of a metal conductive substrate and an oxide film, wherein the oxide film is of a high-entropy structure and is a high-entropy mixed oxide film formed by ruthenium oxide, manganese oxide, stannic oxide, tantalum oxide, cobalt oxide, zirconium oxide, titanium oxide and antimony oxide. The preparing method includes steps of brush coating, drying, thermal oxidation treatment and cooling. The high-entropy mixed oxide electrode material has high specific capacitance and is suitable for preparing high-performance super-capacitors. In addition, the method for preparing the high-entropy mixed oxide electrode material is simple in process, convenient to operate and suitable for being applied to large-scale production.
Description
Technical field
The present invention relates to a kind of high entropy mixed oxide electrode material and preparation method thereof.This oxide electrode material is mainly used in electrochemical capacitor and uses as energy storage electrode.
Background technology
Ruthenium-oxide has very high theory than electric capacity, and theory is generally considered one of desirable electrochemical capacitor electrode material more than thinking and can reaching 1300F/g.But in fact, from the prior art, adopt ruthenium-oxide as electrode material, face two conflicting problems: if the ruthenium oxide electrode material that adopts technological means capable of being industrialized to prepare, as thermal spraying, plasma spraying technology, institute obtainable very more limited than electric capacity, generally at 150F/g between 300F/g; If adopt hydro thermal method, chemical precipitation method etc., although can realize high capacitance, there is the technical problem of complex process, process conditions harshness, be difficult to realize suitability for industrialized production, thereby practicality is not strong.
The ruthenium-oxide that different technique is prepared or containing ruthenium-oxide combination electrode material, can show diverse chemical property.This comes from electrode prepared by different process or has electrode material prepared by different combination formulas has diverse institutional framework.Research shows that the energy storage of electrode material is affected by the specific area of electrode, the institutional framework defect of electrode and the dispersiveness of ruthenium-oxide mainly.Therefore, address the above problem, improve dispersiveness, increase ruthenium-oxide or the defect sturcture containing ruthenium-oxide electrode coating of ruthenium-oxide in electrode, and the specific area of increase electrode coating be key technology.Up to the present, also there is no a simple and effective result of the above problems industrial.
Summary of the invention
In order to address the above problem, inventor of the present invention concentrates on the focus of research the defect sturcture that how improves electrode by simple and effective way, and the dispersiveness that improves ruthenium-oxide starts with, through well-designed, research repeatedly, the way of the problems referred to above that achieve a solution.The invention provides a kind of high entropy mixed oxide electrode material and preparation method thereof.Electrode material of the present invention is made up of the different oxide of multiple crystal structure, because the difference on crystal structure, cause having highdensity fault of construction in mixed oxide film, there is high entropy structure (high randomness), be therefore referred to as high entropy mixed oxide electrode material.Again because the proportional control of ruthenium-oxide total oxide 40% in, and evenly mix, therefore ruthenium-oxide has very high dispersiveness.Result of the test shows, this electrode shows very high capacitive property, approaches theoretical value than electric capacity; And the technology of preparing adopting is simple, repeatable strong, be suitable for suitability for industrialized production.
For reaching above-mentioned object, the present invention adopts following technical scheme:
A kind of high entropy mixed oxide electrode material, is made up of metallic conduction matrix and sull.Described sull has high entropy structure, the high entropy mixed oxide film being made up of ruthenium-oxide, manganese oxide, tin oxide, tantalum oxide, cobalt oxide, zirconia, titanium oxide, these 8 kinds of oxides of antimony oxide.
In described high entropy mixed oxide film, contain: ruthenium-oxide 10mol%～40mol%, manganese oxide 5mol%～20mol%, tin oxide 5mol%～20mol%, tantalum oxide 5mol%～20mol%, cobalt oxide 5mol%～20mol%, zirconia 5mol%～20mol%, titanium oxide 5mol%～20mol%, antimony oxide 5mol%～20mol%.
Described metallic conduction matrix is any one in titanium, titanium alloy, stainless steel, tantalum, nickel, vanadium.
A preparation method for high entropy mixed oxide electrode material, comprises the steps:
1) ruthenium trichloride that is 10～40% by molar percentage, 5～20% titanium trichloride, 5～20% butter of tin or stannous chloride, 5～20% tantalic chloride, 5～20% manganese chloride, 5～20% cobalt chloride, 5～20% zirconium chloride, 5～20% antimony chloride are dissolved in ethanolic solution, employing supersonic oscillations are even, total metal ion in solution is controlled at 0.1～0.4mol/L concentration, makes hybrid metal chloride precursor solution;
2) by the brushing of hybrid metal chloride precursor solution at metallic conduction matrix surface, adopt infrared baking solidify, then put into Muffle furnace and carry out thermal oxidation; Thermal oxidation temperature is 250～400 DEG C, thermal oxidation is come out of the stove cooling after 8～15 minutes, then repeat " brushing, oven dry, thermal oxidation, cooling " step, until all precursor solution is finished, finally in Muffle furnace, anneal 0.5～2 hour, come out of the stove after cooling and make high entropy mixed oxide electrode material.
The invention has the beneficial effects as follows: the ratio electric capacity of high entropy mixed oxide electrode material of the present invention reaches as high as 1158F/g, and the theory that approaches very much ruthenium-oxide compares electric capacity.And the method for the high entropy mixed oxide of the preparation electrode material adopting is simple, easy to operate, be suitable for suitability for industrialized production application.
Embodiment
The following stated is only preferred embodiment of the present invention, and all equivalent variations of doing according to the present patent application the scope of the claims and modification all should belong to covering scope of the present invention.
Embodiment 1
The high entropy mixed oxide of the one electrode material of the present embodiment, is made up of Titanium conducting base and high entropy mixed oxide film.Described high entropy mixed oxide film is by ruthenium-oxide 10mol%, manganese oxide 10mol%, tin oxide 20mol%, tantalum oxide 20mol%, cobalt oxide 10mol%, zirconia 5mol%, these 8 kinds of mixed oxides that oxide forms of titanium oxide 20mol%, antimony oxide 5mol%.Its preparation method comprises the following steps:
1) by ruthenium trichloride (molar percentage 10%), manganese chloride (molar percentage 10%), butter of tin or stannous chloride (molar percentage 20%), tantalic chloride (molar percentage 20%), cobalt chloride (molar percentage 10%), zirconium chloride (molar percentage 5%), titanium trichloride (molar percentage 20%), trichloride antimony (molar percentage 5%) is dissolved in ethanolic solution, employing supersonic oscillations are even, total metal ion in solution is controlled at 0.2mol/L concentration, make hybrid metal chloride precursor solution.
2) by the brushing of hybrid metal chloride precursor solution at titanium matrix surface, adopt infrared baking solidify, then put into Muffle furnace and carry out thermal oxidation; Thermal oxidation temperature is 250 DEG C, and thermal oxidation is come out of the stove cooling after 15 minutes, then repeats brushing, oven dry, thermal oxidation, cooling step, until all precursor solution is finished, finally in Muffle furnace, anneal 2 hours, the air cooling of coming out of the stove, makes high entropy mixed oxide electrode material.
Embodiment 2
The high entropy mixed oxide of the one electrode material of the present embodiment, is made up of metallic nickel conducting base and high entropy mixed oxide film.Described high entropy mixed oxide film is by ruthenium-oxide 20mol%, manganese oxide 20mol%, tin oxide 5mol%, tantalum oxide 5mol%, cobalt oxide 20mol%, zirconia 20mol%, these 8 kinds of mixed oxides that oxide forms of titanium oxide 5mol%, antimony oxide 5mol%.Its preparation method comprises the following steps:
1) ruthenium trichloride (molar percentage 20%), manganese chloride (molar percentage 20%), butter of tin or stannous chloride (molar percentage 5%), tantalic chloride (molar percentage 5%), cobalt chloride (molar percentage 20%), zirconium chloride (molar percentage 20%), titanium trichloride (molar percentage 5%), antimony chloride (molar percentage 5%) are dissolved in ethanolic solution, employing supersonic oscillations are even, total metal ion in solution is controlled at 0.3mol/L concentration, makes hybrid metal chloride precursor solution.
2) by the brushing of hybrid metal chloride precursor solution on metallic nickel conducting base surface, adopt infrared baking solidify, then put into Muffle furnace and carry out thermal oxidation; Thermal oxidation temperature is 300 DEG C, thermal oxidation is come out of the stove cooling after 10 minutes, then repeat " brushing, oven dry, thermal oxidation, cooling " step, until all precursor solution is finished, finally in Muffle furnace, anneal 1.5 hours, the air cooling of coming out of the stove, makes high entropy mixed oxide electrode material.
Embodiment 3
The high entropy mixed oxide of the one electrode material of the present embodiment, is made up of metal tantalum conducting base and high entropy mixed oxide film.Described high entropy mixed oxide film is by ruthenium-oxide 30mol%, manganese oxide 5mol%, tin oxide 10mol%, tantalum oxide 10mol%, cobalt oxide 5mol%, zirconia 10mol%, these 8 kinds of mixed oxides that oxide forms of titanium oxide 10mol%, antimony oxide 20mol%.Its preparation method comprises the following steps:
1) by ruthenium trichloride (molar percentage 30%), manganese chloride (molar percentage 5%), butter of tin or stannous chloride (molar percentage 10%), tantalic chloride (molar percentage 10%), cobalt chloride (molar percentage 5%), zirconium chloride (molar percentage 10%), titanium trichloride (molar percentage 10%), antimony chloride (molar percentage 20%) is dissolved in ethanolic solution, employing supersonic oscillations are even, total metal ion in solution is controlled at 0.4mol/L concentration, make hybrid metal chloride precursor solution.
3) by the brushing of hybrid metal chloride precursor solution at tantalum matrix surface, adopt infrared baking solidify, then put into Muffle furnace and carry out thermal oxidation; Thermal oxidation temperature is 350 DEG C, and thermal oxidation is come out of the stove cooling after 8 minutes, then repeats brushing, oven dry, thermal oxidation, cooling step, until all precursor solution is finished, finally in Muffle furnace, anneal 1 hour, the air cooling of coming out of the stove, makes high entropy mixed oxide electrode material.
Embodiment 4
The high entropy mixed oxide of the one electrode material of the present embodiment, is made up of vanadium metal conducting base and high entropy mixed oxide film.Described high entropy mixed oxide film is by ruthenium-oxide 40mol%, manganese oxide 15mol%, tin oxide 5mol%, tantalum oxide 5mol%, cobalt oxide 5mol%, zirconia 5mol%, these 8 kinds of mixed oxides that oxide forms of titanium oxide 15mol%, antimony oxide 10mol%.Its preparation method comprises the following steps:
1) ruthenium trichloride (molar percentage 40%), manganese chloride (molar percentage 15%), butter of tin or stannous chloride (molar percentage 5%), tantalic chloride (molar percentage 5%), cobalt chloride (molar percentage 5%), zirconium chloride (molar percentage 5%), titanium trichloride (molar percentage 15%), antimony chloride (molar percentage 10%) are dissolved in ethanolic solution, employing supersonic oscillations are even, total metal ion in solution is controlled at 0.3mol/L concentration, makes hybrid metal chloride precursor solution.
2) the vanadium matrix surface in the processing of process roughening by the brushing of hybrid metal chloride precursor solution, adopts infrared baking to solidify, and then puts into Muffle furnace and carries out thermal oxidation; Thermal oxidation temperature is 400 DEG C, and thermal oxidation is come out of the stove cooling after 10 minutes, then repeats brushing, oven dry, thermal oxidation, cooling step, until all precursor solution is finished, finally in Muffle furnace, anneal 0.5 hour, the air cooling of coming out of the stove, makes high entropy mixed oxide electrode material.
Below in conjunction with the test result to high entropy mixed oxide electrode material, beneficial effect of the present invention is described.The ratio capacitive property of high entropy oxide electrode material adopts standard three electrode test systems to test, and is platinum electrode to electrode, and reference electrode is saturated calomel electrode, and electrolyte is 0.5mol/L H
2sO
4the aqueous solution.Table 1 has provided the capacitive property of high entropy oxide electrode material prepared by each embodiment.As can be seen from Table 1, the ratio electric capacity difference to some extent of the high entropy mixed oxide electrode material that different embodiment obtain, but all there is very high ratio capacitance.Wherein the ratio electric capacity of the prepared electrode material of embodiment tri-is up to 1158F/g.This capacitance is rare in the prior art.This has fully demonstrated the performance advantage of high entropy mixed oxide electrode material.In addition, the very important point is that preparation method provided by the invention has advantages of that technique is simple, can repeat, be applicable to large-scale production.Application of the present invention not only, to promoting material technology, especially promotes high entropy oxide material technology of preparing and has important facilitation, and the technology of preparing of high specific capacitance ultracapacitor is also had to positive facilitation.Therefore, the present invention has very important social value and economic worth.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Than electric capacity (F/g) | 781.1 | 1013 | 1158 | 805.7 |
Claims (3)
1. one kind high entropy mixed oxide electrode material, formed by metallic conduction matrix and sull, it is characterized in that: described sull has high entropy structure the high entropy mixed oxide film being formed by ruthenium-oxide, manganese oxide, tin oxide, tantalum oxide, cobalt oxide, zirconia, titanium oxide, these 8 kinds of oxides of antimony oxide;
In described high entropy mixed oxide film, contain: ruthenium-oxide 10 mol%～40 mol%; Manganese oxide 5 mol%～20 mol%, tin oxide 5 mol%～20 mol%, tantalum oxide 5 mol%～20 mol%, cobalt oxide 5 mol%～20 mol%, zirconia 5 mol%～20 mol%, titanium oxide 5 mol%～20 mol%, antimony oxide 5 mol%～20 mol%.
2. high entropy mixed oxide electrode material according to claim 1, is characterized in that: described metallic conduction matrix is any one in titanium, titanium alloy, stainless steel, tantalum, nickel, vanadium.
3. a high-temperature thermal oxidation preparation method for high entropy mixed oxide electrode material as claimed in claim 1, is characterized in that comprising the steps:
1) ruthenium trichloride that is 10～40% by molar percentage, 5～20% titanium trichloride, 5～20% butter of tin or stannous chloride, 5～20% tantalic chloride, 5～20% manganese chloride, 5～20% cobalt chloride, 5～20% zirconium chloride, 5～20% antimony chloride are dissolved in ethanolic solution, employing supersonic oscillations are even, total metal ion in solution is controlled at 0.1～0.4mol/L concentration, makes hybrid metal chloride precursor solution;
2) by the brushing of hybrid metal chloride precursor solution at metallic conduction matrix surface, adopt infrared baking solidify, then put into Muffle furnace and carry out thermal oxidation; Thermal oxidation temperature is 250～400 DEG C, thermal oxidation is come out of the stove cooling after 8～15 minutes, then repeat brushing, oven dry, thermal oxidation, cooling step, until all precursor solution is finished, finally in Muffle furnace, anneal 0.5～2 hour, come out of the stove after cooling and make high entropy mixed oxide electrode material.
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| CN103088370B (en) * | 2011-11-08 | 2015-06-03 | 攀钢集团研究院有限公司 | Method for purifying metallic titanium from cathode product obtained by molten salt electrolysis |
| CN102915853B (en) * | 2012-08-23 | 2015-06-03 | 云南大学 | RuO2-SnO2-TiO2-Ta2O5/Ta cathode piece and preparation method thereof |
| CN107416940B (en) * | 2017-05-19 | 2020-04-10 | 福州大学 | Ir doped titanium dioxide electrode material with heterogeneous photoelectrocatalysis performance |
| CN107162115B (en) * | 2017-05-19 | 2020-03-10 | 福州大学 | Application of Ir-doped titanium-based stannic oxide electrode with photoelectrocatalysis performance in degradation of organic wastewater |
| CN107162116B (en) * | 2017-05-19 | 2020-04-10 | 福州大学 | Ru-doped titanium dioxide electrode material with heterogeneous photoelectrocatalysis performance |
| CN114959340B (en) * | 2022-05-18 | 2023-01-03 | 哈尔滨工业大学 | Multi-principal-element oxide dispersion-strengthened superfine-crystal aluminum-based composite material and preparation method thereof |
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| CN101048535A (en) * | 2004-09-01 | 2007-10-03 | 埃尔塔克***公司 | PD-containing coating for low chlorine overvoltage |
| CN101665948A (en) * | 2009-09-18 | 2010-03-10 | 天津大学 | Dinitrogen pentoxide electrode on electrochemistry synthesis and preparation method thereof |
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